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WO2019082427A1 - Matériau d'acier inoxydable ayant une excellente performance de prévention d'apparition de taches de laitier, élément structurel soudé et son procédé de production - Google Patents

Matériau d'acier inoxydable ayant une excellente performance de prévention d'apparition de taches de laitier, élément structurel soudé et son procédé de production

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Publication number
WO2019082427A1
WO2019082427A1 PCT/JP2018/018480 JP2018018480W WO2019082427A1 WO 2019082427 A1 WO2019082427 A1 WO 2019082427A1 JP 2018018480 W JP2018018480 W JP 2018018480W WO 2019082427 A1 WO2019082427 A1 WO 2019082427A1
Authority
WO
WIPO (PCT)
Prior art keywords
cao
mno
stainless steel
slag
steel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/018480
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English (en)
Japanese (ja)
Inventor
靖弘 江原
森田　一成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Nisshin Co Ltd
Original Assignee
Nisshin Steel Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nisshin Steel Co Ltd filed Critical Nisshin Steel Co Ltd
Priority to KR1020207014455A priority Critical patent/KR102391566B1/ko
Priority to CN201880068466.1A priority patent/CN112218965A/zh
Publication of WO2019082427A1 publication Critical patent/WO2019082427A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K31/00—Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by only one of the preceding main groups
    • B23K31/02—Processes relevant to this subclass, specially adapted for particular articles or purposes, but not covered by only one of the preceding main groups relating to soldering or welding
    • B23K31/027—Making tubes with soldering or welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3053—Fe as the principal constituent
    • B23K35/308—Fe as the principal constituent with Cr as next major constituent
    • B23K35/3086—Fe as the principal constituent with Cr as next major constituent containing Ni or Mn
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0006—Adding metallic additives
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese

Definitions

  • the present invention relates to a stainless steel material that is less likely to generate a defect called "slag spot” or "black spot”, which is a type of welding defect that occurs in arc welding beads.
  • the present invention also relates to a welded structural member using the steel material and a method of manufacturing the same.
  • slag spot When arc welding is performed using a stainless steel material as a base material, a defect called "slag spot" in which oxide aggregates are scattered on the weld bead may occur.
  • the appearance photograph of the weld bead which the slag spot which is published in the nonpatent literature 1 which arose in FIG. 1 is quoted and illustrated.
  • the slag spot is a minute slag which floats in the form of islands or spots at intervals of several mm to several cm on the weld bead.
  • FIG. 2 illustrates the appearance of a slag spot found on the weld bead of a steel pipe produced by TIG welding.
  • the number of slag spots per 1 m in the bead length direction (hereinafter referred to as “slag spot generation rate”) of slag spots having a major diameter of 1.0 mm or more found in this steel pipe was 0.7 piece / m.
  • Patent documents 1 and 2 are ferritic stainless steels in which the generation of slag spots (black spots) is reduced by adjusting the content of easily oxidizable elements Al, Ti, Si and Ca to an optimized steel composition. Is disclosed. However, according to the inventors' investigation, the effect of suppressing the slag spot is limited only by adjusting the steel composition, and there is room for further improvement.
  • Patent Document 3 describes that, in an austenitic Fe-Ni-Cr alloy for a cladding tube, foreign matter on the surface of a welded portion, which is a starting point of processing cracking, is reduced.
  • the foreign matter adhering to the surface of the weldment is mainly composed of oxides or nitrides such as Al, Ti, Si, Ca, and Mg, and nonmetallic inclusions present in the base material generally have a high melting point, It is taught that when welding, it does not melt, floats on the surface of the molten metal, condenses, and solidifies, it remains on the surface as it is to form irregularities (paragraph 0035).
  • the foreign matter attached to the surface of the welded portion is derived from nonmetallic inclusions present in the base material (paragraph 0038).
  • the technique disclosed in Patent Document 3 in addition to reducing the amounts of Al, Ti, and Si as much as possible, they are present in the base material by reducing other inclusion constituent elements Ca, Mg, N, and O. Reduce the number of inclusions, thereby reducing foreign matter observed on the surface of the weld metal (paragraph 0039).
  • the method of using a welding wire for an electrode, and the method of adding a filler metal are mentioned. It is also effective to use fluxed welding wire.
  • arc welding using non-soldering electrodes, such as TIG welding is widely performed, and in many cases, no filler metal is used.
  • the present invention does not rely on the use of a welding wire or a filler metal, and even when non-electrode arc welding is employed, generation of slag spots is stable with various types of stainless steel regardless of whether austenitic or ferritic. To provide a technology that can be significantly suppressed.
  • the inventors in addition to reducing the amount of non-metallic inclusions present in the stainless steel base material, in particular by adopting a method of controlling the composition of oxide-based inclusions, We have found that the above tasks can be achieved.
  • the present invention discloses the following inventions.
  • a base material for arc welding made of the stainless steel material according to the above [1].
  • a steel plate base material for arc welded pipe making which is made of the stainless steel material according to the above [1].
  • a method for producing a welded steel pipe using a steel plate which is the stainless steel material described in the above-mentioned [1] as a base material and forming a welded steel pipe by non-smelting electrode type arc welding without adding a filler metal.
  • the content of each of the above-described steel components is the total content of the elements present in the steel. Therefore, the content of the metal element or oxygen partially present as an oxide includes the amount present as an oxide.
  • the average CaO / (SiO 2 + MnO + CaO) mass ratio of the oxide inclusions and the average CaO / MnO mass ratio can be determined as follows.
  • the arc welded structural member is a member having a weld formed by arc welding.
  • the arc welded steel pipe is a steel pipe having a weld formed by arc welding. These welds can be "welded parts without filler addition" (i.e. welds formed without the addition of filler).
  • the contents of Si, Mn, Ca, Al, Mg, Ti, Cr and Fe are respectively as oxide SiO 2 , MnO, CaO, Al 2 O 3 , MgO, TiO 2 , Cr 2 O 3 and FeO Converted to the mass proportion of SiO 2 , MnO and CaO in these eight oxides, respectively, the SiO 2 content (mass%), the MnO content (mass%) and the CaO content of the particles concerned (Mass%)
  • the average content (% by mass) of SiO 2 , MnO and CaO for all the measurement particles is calculated.
  • the average CaO / (SiO 2 + MnO + CaO) mass ratio is determined by substituting the value of the above-mentioned average content (mass%) of the oxide concerned in the part of the chemical formula of each of the following formula (1).
  • an average CaO / MnO mass ratio is determined by substituting the value of the above-mentioned average content (mass%) of the oxide concerned into a part of a chemical formula of each oxide of the following formula (2).
  • This technology can be applied to various stainless steel types, regardless of austenite type or ferrite type, and is particularly effective in TIG welding performed without adding a filler metal.
  • Component composition of steel In the present invention, various steel types are applicable regardless of austenite type or ferrite type. According to the inventors' investigation, the suppression effect of the slag spot by the below-mentioned inclusion composition control is acquired in the following composition ranges.
  • Ni, Mo, Cu, Nb, V, Zr, W, Co, B, Ti, Al, Ca, Mg, REM (a rare earth element other than Y), and Y are arbitrarily contained elements.
  • the following pattern can be considered as a generation factor of the slag spot which arises in the arc welding bead which used stainless steel materials as a base material.
  • the oxidizable element (Al, Ca, Ti, etc.) in the base material forms an oxide at a portion where the gas shield is insufficient and remains on the bead.
  • Patent 1 Non-metallic inclusions with high dissociation temperature present in the base material agglomerate and float along with the sweep of the arc, and when the agglomerated particles become large to some extent, they are left from the sweep of the arc and remain on the bead. According to the inventors' investigations, slag spots are generated even when the gas shielding is sufficiently performed.
  • the generation factor of the pattern 2 is used. It is necessary to overcome.
  • the generation factor of the pattern 1 can be eliminated by limiting the content of the oxidizable element and the like in the steel composition of the base material to the above-mentioned range.
  • the inclusion control in the base material is important.
  • the cause of slag spots is oxide inclusions having a high dissociation temperature.
  • SiO 2 , MnO, CaO, Al 2 O 3 , MgO and the like can be mentioned as typical components of the oxide inclusions present in the steel material.
  • CaO is not reduced even at the time of welding because it has a high dissociation temperature and remains as an oxide. As it agglomerates in the molten metal due to the heat of the arc, it appears as a slag spot after cooling.
  • MnO and SiO 2 have a relatively low dissociation temperature, Mn and Si constituting the oxide are reduced at the time of welding to form a metal and easily dissolve in the molten metal. Therefore, MnO and SiO 2 are less likely to be a cause of generation of slag spots.
  • SiO 2 -CaO type a general type oxide inclusion having a high content of SiO 2 and CaO
  • composition control of the inclusion decreases the Ca concentration and increases the Mn concentration.
  • oxide inclusions of the illustrated type are referred to as "SiO 2 -MnO-CaO type" for convenience.
  • Metal oxides generally dissociate into metal and oxygen as the temperature increases. For example, when assuming the partial pressure of oxygen at 10 ⁇ 12 atm in Elingham diagram, the dissociation temperature is estimated: SiO 2 : about 1530 ° C., MnO: about 1380 ° C., CaO: about 2100 ° C., Al 2 O 3 : about 2020 It will be ° C.
  • the inclusion of SiO 2 -CaO type advantageously as possible by changing the SiO 2 -MnO-CaO type, i.e. be a composition of inclusions relatively SiO 2 -MnO-CaO type dominance, suppression of slag spot It becomes.
  • Al 2 O 3 has a high dissociation temperature, steel materials adjusted to the above-described steel composition are less likely to cause slag spots because the amount of Al 2 O 3 is small.
  • the present invention employs an "average CaO / MnO mass ratio". As this value is smaller, it can be evaluated that the inclusion composition is relatively dominated by the SiO 2 -MnO-CaO type, which is advantageous to suppression of the occurrence of the slag spot.
  • the average CaO / MnO mass ratio can be determined by the method described above.
  • the average CaO / MnO mass ratio is more preferably 10.0 or less, and may be controlled to 6.0 or less.
  • an inclusion composition having an average CaO / (SiO 2 + MnO + CaO) mass ratio of 0.40 or less.
  • the average CaO / (SiO 2 + MnO + CaO) mass ratio can be determined by the method described above.
  • the above-mentioned stainless steel material in which the average CaO / (SiO 2 + MnO + CaO) mass ratio of oxide inclusions and the average CaO / MnO mass ratio are optimized, is manufactured using a general stainless steel melting facility be able to. Typically, VOD process and AOD process can be mentioned. In any case, first, decarburization in which oxygen is blown into the Cr-containing molten iron is applied, and a molten steel having a Cr oxide-containing slag on the hot water surface (C content is, for example, 0.20% or less) is manufactured by a conventional method.
  • the molten steel at this stage is a de-carburized steel into which oxygen is blown, the oxidizable elements Si, Ti, Al, Ca, Mg and the like are oxidized and removed from the molten steel. That is, Si, Ti, Al, Ca and Mg are hardly present in the molten steel.
  • a part of Cr contained in a large amount in the molten steel is also oxidized to form a slag on the surface of the molten steel as Cr oxide.
  • the molten steel contains a large amount of dissolved oxygen blown for decarburization. Therefore, it is necessary to deoxidize before casting. Final composition adjustments are made using FeSi alloys rather than Al as the deoxidizer.
  • (1) Refinement is performed so that the oxygen content in the steel (total oxygen content including oxygen present as an oxide) is 0.0030% (30 ppm) or more.
  • the oxygen content is less than 0.0030%, it becomes difficult to refine the average CaO / MnO mass ratio stably to 15.0 or less.
  • it is more preferable to adjust the oxygen content to be 0.0040% (40 ppm) or more.
  • the oxygen content is too high, a large amount of inclusions having a high Cr oxide content is generated, which is a factor causing deterioration of the product quality.
  • the oxygen content is limited to 0.0150% (150 ppm) or less, and more preferably 0.0100% (100 ppm) or less. It may be controlled to 0.0060% (60 ppm) or less.
  • Si deoxidation is performed using a high purity FeSi alloy having a Ca content of, for example, 0.20% or less.
  • Slag basicity CaO / SiO 2 is adjusted to a range of 1.20 to 1.60.
  • the stainless steel shown in Table 1 was melted using a VOD process to obtain a continuously cast slab.
  • inclusion control was attempted by changing the total oxygen content in the steel, the type of FeSi alloy as a deoxidizer, and the condition of slag basicity (CaO / SiO 2 ).
  • Table 2 shows each condition.
  • the oxygen content in Table 2 is the value shown in Table 1 again.
  • As the FeSi alloy which is a deoxidizer high-purity products having a small amount of impurities and normal products were used.
  • the high purity product is one in which the Ca content is reduced to 0.20 mass% or less.
  • the Ca content of the normal product is about 0.5 to 1.5% by mass.
  • the slag basicity was determined by analyzing a sample collected from the slag.
  • a cold-rolled and annealed steel sheet with a thickness of 0.5 to 1.5 mm was obtained in a process including hot rolling and cold rolling.
  • SEM scanning electron microscope
  • observation is performed on a cross section (L cross section) parallel to the rolling direction and thickness direction of this cold rolled annealed steel sheet, and an oxide system is obtained by EDX (energy dispersive X-ray analysis) attached to the SEM Composition analysis of inclusions was performed.
  • Welded steel pipes were manufactured under normal conditions by TIG welding using each cold rolled annealed steel sheet as a raw material.
  • the outer diameter of the tube is in the range 25-51 mm. No filler metal was added during welding.
  • Samples were randomly drawn from the obtained steel pipe products, and the occurrence of slag spots was investigated for continuous weld beads of 50 m or more in length.
  • the number of slag spots having a major axis (diameter of the longest portion of the particles) of 1.0 mm or more was counted, and the number of generated slag spots per 1 m was regarded as the slag spot generation rate (piece / m).
  • the slag spot generation rate of the said size is 0.30 piece / m or less, it can be evaluated that generation
  • the steel composition of the present invention example in which the steel composition satisfies the specified range of the present invention and the average CaO / (SiO 2 + MnO + CaO) mass ratio of the oxide inclusions and the average CaO / MnO mass ratio is controlled within the specified range of the present invention is There is very little occurrence of slag spots.
  • FIG. 3 shows the relationship between the average CaO / (SiO 2 + MnO + CaO) mass ratio of the oxide inclusions and the slag spot generation rate for each example.
  • the black circle plot is an example using “high purity product” as the deoxidizer FeSi alloy, and the white circle plot is an example using “normal product” (same in FIGS. 4 to 9 below).
  • inclusion and a slag spot generation rate is shown in FIG. 4, FIG. 5 about each case.
  • FIG. 5 is an enlarged view of the region where the average CaO / MnO mass ratio in FIG. 4 is low.
  • FIG. 6 The relationship between the total oxygen content in steel materials and the average CaO / MnO mass ratio of oxide inclusions is shown in FIG. 6 and FIG. 7 for each example.
  • FIG. 7 is an enlarged view of the region where the average CaO / MnO mass ratio in FIG. 6 is low. It can be seen that setting the oxygen content to 0.0030% or more is extremely effective in controlling the average CaO / MnO mass ratio of oxide inclusions to a low level.
  • FIG. 8 shows the relationship between the total oxygen content in the steel material and the slag spot generation rate for each example. It turns out that it is effective in generation
  • FIG. 9 shows the relationship between the slag basicity and the slag spot generation rate during refining. It can be seen that using a “high purity product” as the deoxidizer FeSi alloy and adjusting the slag basicity to a range of 1.20 to 1.60 is effective in suppressing the generation of slag spots.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Steel In Its Molten State (AREA)

Abstract

Le matériau d'acier inoxydable selon la présente invention peut éviter de façon stable et nette l'apparition de taches de laitier pendant un soudage à l'arc, le matériau d'acier inoxydable ayant une composition chimique qui contient, en termes de % en masse, 0,005 à 0,100 % de C, 0,10 à 3,00 % de Si, 0,10 à 6,50 % de Mn, 0,001 à 0,050 % de P, 0,0001 à 0,0200 % de S, 0 à 20,00 % de Ni, 10,50 à 26,00 % de Cr, 0,005 à 0,200 % de N, 0,0030 à 0,0150 % d'O et, si nécessaire, des quantités prescrites de Mo, Cu, Nb, V, Zr, W, Co, B, Ti, Al, Ca, Mg, terres rares (à l'exclusion de Y) et Y, le reste comprenant du Fe et des impuretés inévitables, le rapport massique CaO/ (SiO 2 + MnO + CaO) moyen étant inférieur ou égal à 0,40 et le rapport massique CaO/MnO moyen étant de 15,0 dans des inclusions à base d'oxyde observées dans la structure en acier.
PCT/JP2018/018480 2017-10-25 2018-05-14 Matériau d'acier inoxydable ayant une excellente performance de prévention d'apparition de taches de laitier, élément structurel soudé et son procédé de production Ceased WO2019082427A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020207014455A KR102391566B1 (ko) 2017-10-25 2018-05-14 슬래그 스폿 발생 억제능이 우수한 스테인리스 강재 및 용접 구조 부재 및 그 제조법
CN201880068466.1A CN112218965A (zh) 2017-10-25 2018-05-14 渣点产生抑制能力优异的不锈钢材和焊接结构构件及其制造方法

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JP2017206555A JP7042057B2 (ja) 2017-10-25 2017-10-25 スラグスポット発生抑止能に優れるステンレス鋼材並びに溶接構造部材およびその製造法
JP2017-206555 2017-10-25

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JP (1) JP7042057B2 (fr)
KR (1) KR102391566B1 (fr)
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EP4112751A4 (fr) * 2020-02-27 2025-06-25 NIPPON STEEL Stainless Steel Corporation Acier inoxydable pour feuilles métalliques, feuille d'acier inoxydable, procédé de production d'acier inoxydable pour feuilles métalliques, et procédé de production de feuille d'acier inoxydable
EP4112753A4 (fr) * 2020-02-27 2025-07-02 Nippon Steel Stainless Steel Corp Acier inoxydable, matériau d'acier inoxydable et procédé de production d'acier inoxydable

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EP4092150A4 (fr) * 2020-01-15 2025-06-18 NIPPON STEEL Stainless Steel Corporation Acier inoxydable ferritique
CN112941403A (zh) * 2021-01-14 2021-06-11 上海欣冈贸易有限公司 一种焊接用无硫低碳钢金属合金及其组合物
CN112826575A (zh) * 2021-03-19 2021-05-25 郑自力 一种穿刺针及其制备工艺和应用
US20250137110A1 (en) * 2021-10-01 2025-05-01 Nippon Steel Corporation Duplex stainless steel pipe
WO2023054599A1 (fr) * 2021-10-01 2023-04-06 日本製鉄株式会社 Tuyau en acier inoxydable duplex
CN115466909B (zh) * 2022-10-26 2023-03-24 浦项(张家港)不锈钢股份有限公司 一种奥氏体不锈钢、制备工艺及应用

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